Synthetic resinous product and process of making same



Fatented Nov. 8, 1927.

UNITED STATES PATENT OFFICE. V

BGEIS It. LOUGOVOY, OF MONTCLAIB, NEW JERSEY, ASSIGNOR TO ELLIS-FOSTER COM- rm, OF MONTGLAIB, NEW JERSEY, A COBPOR-ATIQN OF NEW JERSEY.

SYNTHETIC BESINOUS PRODUCT AND PROCESS OF MAKING SAME.

27o Brewing.

This invention relates to a synthetic resinous product and to the process of making same and relates especial y to resinous material obtained by reacting on a dyestufi with an aldehyde such as formaldehyde.

The dyestufi which I employ is prepared b reacting on benzotrichloride or side-chain clilorinated toluol with a phenolic body such as commercial carbolic acid or ordinary phenol, also tar acids, cres lic acid, ortho, meta and para cresols, xy enols etc. The proportion of the chlorinated material and the phenol may be varied somewhat but preferabl I employ a proportion represented by 1 mo of benzotrichloride to 3 mols. of the phenolic body. In any event I prefer to not employ any excess of the phenol as I wish to have no free flphenolic body present in the finished dyestu The reaction with the lower phenols takes place very vigorously. For example in heating in a flask under reflux condenser a mixture of carbolic acid and benzotrichloride in i the above proportions the reaction may start so vi orously that the contents of the flask will e projected through the condenser. This is robably due to the very rapid evolution of hydrochloric acid. The reaction takes lace in a more quiet manner in the case for example orthocresol. On gently warming an ort ocresol mixture reaction starts and the source of heat then may be removed. The reaction goes on spontaneously with the evolution of heat until a considerable proportion of the chlorine has been expelled as hydrochloric acid. Heat then may be applied and the remainder of the chlorine present in the side-chain practicalliy completely expelled as hydrochloric eci The reaction carried out in these propor-- tions or in approximately these proportions yields a somewhat reddish dyestufi usually in the form of a thick syrup or what may be termed a semi-liquid. Unlike the corrosive carbolic acid which for example may have been used in makin the dyestufit' the resulting material when reed from hydrochloric acid is not of a corrosive acid charactor but is totally distinct and different from either of the raw materials employed. Both the benzotrichloride and the carbolic acid are very vicious caustic and dangerous Application filed October 23, 1924. Serial No. 743,386.

substances but when brought together the virulence of each is destroyed by attack on the'other and a mild neutral non-phenolic substance results which I have found from.. I. working with it extensively has no corro- It is true that the dyestufi has .a V

The dyestufl' has the property of reacting with aldehydes particularly formaldehyde "to produce a hard resin even though the formaldehyde is used in very small proportion. I call attention to this noteworthy fact because in making resins from phenol and formaldehyde in the usual way a large proportion of formaldehyde is required. In producing resins from urea a very substantial amount of formaldehyde is called for. The same is true of resins prepared by the reaction of formaldehyde on acetone, aniline and other substances. Formaldehyde is a well known resinifyin agent but it is generally understood in t e synthetic resin industry that a large proportion of it must be used to secure a suitable resin. Also since formaldehyde frequently is the most expensive constituent the use of so large a proportion of formaldehyde considerably increases the cost of manufacture.

However since only a few per cent of actual formaldehyde sufiices in the case of the present invention to yield a resin of useful qualities I am not put to the expense necessitated in producing the more costly products now industrially made from phenol and formaldehyde, urea and formaldehyde and the like.

A further feature is the fact that formaldehyde fluctuates a good bit in price whereas chlorine is more stable in this respect and side-chain chlorinated toluol can be readily prepared from materials which are most abundant.

The dyestufi' which as indicated does not respond to the usual tests for phenol shows various dissimilarities with respect to phenol. Although phenol and chlorinated toluol are used in the preparation the product chemibe removed and handled while still hot.

The striking feature about my dyestufi resin is that it will become converted into a heat-setting or thermo-rigid body without the employment of the inordinate amounts of formaldehyde or hexamethylenetetramine, or mixtures of the two, now employed in the case of the phenol-formaldehyde resins, the urea-formaldehyde resins, the acetone-formaldehyde resins and others. I am therefore of the opinion that the dyestuffs has a molecular structure or composition radically different from any resinous substance heretofore proposed for use in the plastic molding industry.

As examples of methods of preparation of the dyestufl' resin the following are given:

Example 1.56.et parts by weight of carbolic acid and 41 parts of side-chain chlorinated toluol (specific gravity 1.34) were mixed and upon gentle heating an exothermic recation took place and hydrogen chloride was evolved. Upon com letion of the exothermic reaction the resu ting solution was heated to boiling for 2 hours under reflux condenser. During the first hour of the heating hydrogen chloride continued to be evolved. A dyestuff of ,a somewhat reddish color, as a syrupy substance was obtained. Toward the end of the boiling Water was given off as evidenced by a spitting and crackling in the reaction vessel. A dark red brown semi-liquid product was obtained, the yield of this product being up to about 155 per cent of the carbolio acid taken. This product was steam distilled to free it from a. small quantity of free carbolic acid still prescut, the loss being 2 per cent.- After this treatment the product obtained-is a tough semi-solid, soluble in organic solvents such as alcohol, acetone and benzol. Its properties resemble those of a dye belonging to the oxycarboquinonic series such as the derivatives of the triphenylmethane group. Upon pro longed heating at an elevated temperature'it gradually hardens into an infusible, insoluble brittle resinous body. The product after steam distillation was then boiled with 25 per cent of its weight of aqueous per cent formaldehyde solution (i. e. 10% of actual formaldehyde. in solution. based on the weight of the intermediate or dyestuff) under a reflux condenser for 1 hour. During the boiling the solution separated into two layers, the lower layer being a dark viscous mass when hot which hardened upon cooling to a lustrous dark somewhat tacky resin having a melting point of between 40 and C. The resin obtained is soluble in organic solvents such as alcohol, acetone, benzol and the like.

A molding composition was prepared using the above resin by dissolving the resin in an equal quantity of alcohol and 10 per cent hexamethylenetetramine was subsequently dissolved in the alcohol solution. A quantity of wood flour equal in weight to that of the resin was impregnated with the alcoholic solution and the composition was then dried in a vacuum dryer. Upon submitting the composition to a hot molding op-, eration a thermo-rigid molded article was obtained which exhibited all the desirable properties required of a commercial molding composition such as'fiowability, finish etc. A molded article prepared from this com osition when compared with a molded artlcle prepared with a phenol-formaldehyde condensation product was found to have one to one and a half times the transverse strength of that of a phenol-formaldehyde resin.

Example 2.158 parts of orthocresol after mixing with 100 parts of chlorinated toluol was placed in a reaction vessel fitted with a reflux condenser and gently heated. An exothermic reaction took place with the evolution of hydrogen chloride and the temperature of the mixture rose due to the heat of reaction to (SO-70 0. Heat was then tap plied andthe solution boiled for 1% to 2 hours. When the temperature of the solution reached 205 C. separation of water occurred as shown by the spitting and crackling taking place in the reaction vessel and also by the condensate running back from the reflux. The product obtained is a dark reddish brown viscous semi-solid, soluble in organic solvents such as alcohol, acetone, benzol and the like. On heating this product for a prolonged period of time at a temperature of 150200 C. it gradually became more viscous but did not solidify to a thermo-rigid body. The product after steam distillation to remove any free cresol present was boiled with 25 per cent of its Weight of 40 per cent formaldehyde solution under reflux for one hour. A dark hard brittle lustrous fusible resin Wasobtained, soluble in organic solvents such as alcohol, benzol, acetone and the like. Upon treatment of the fusible resin with 1.0 per cent of its weight of hexamethylenetetramine an insoluble but still fusible resinous product was obtained.

What I claim is l. The process of reacting on a corrosive phenol with benzotrichloride to form a substantially non-corrosive dyestuff-containing, material. steam distilling this product and resinifying the latter with an amount of formaldehyde equal to not substantially above one tenth of the weight of said dyestufi-containing material.

2. The process of reacting on aphenol with side-chain-chlorinated toluol to form a substantially non-corrosive dyestufl-containing material, steam distillin this product and resinifying the latter wit an amount of formaldehyde equal to not substantially above one tenth of the weight of said dyestufi-containing material.

3. The process which comprises reactin with benzotrichloride approximately one mo 1 on carbolic acid approximately three mols. to form a substantially non-corrosive red dyestufi', steam distilling to remove any unchanged carbolic acid, heating to increase the consistency, resinifying by treatment with aqueous formaldehyde in the presence of an acid substance, purifying the resulting resin and incorporating with it a small pro portion of hexamethylenetetramine.

4. A process which comprises reacting upon a phenol with side-chain-chlorinated toluol, to form a substantially non-corrosive dyestufl-containing material, removing ex- 'tainin cess of the phenol b steam distillation and reacting upon the ye-conta'ining material with a small amount of formaldehyde.

5..A process which comprises reacting upon a phenol with benzotrichloride to form a substantially non-corrosive dyestufi-con tainin material, removing excess of the phenol by steam distillation and reacting uponthe dye-containin material with a small amountof formaldehyde.

6. A process which comprisesreactin upon a phenol with side-chainhlorinate toluol, to form a substantially non-corrosive dyestufi-containing material, removing excess of the phenol and reacting upon the dyestufl-containing material with a small amount of formaldehyde. a,

7. A process which com rises reacting upon a phenol with 'benzotric loride to form a substantially non-corrosive dyestufi-conv taining material, removin excess of the phenol and reacting upon t e dyestufi-conmaterial with a small amount of forma dehyde. 7

BORIS N. LOUGOVOY." 

